Nitric Acid → HCID 11614252, compound

HRID 1028578Notes

Reaction equation

HRID 1028578 reaction equation
[F:1][C:2]([F:40])([F:39])[C:3]1[CH:4]=[C:5]([C@H:13]2[O:17][C:16](=[O:18])[N:15]([CH2:19][C:20]3[CH:25]=[C:24]([C:26]([F:29])([F:28])[F:27])[CH:23]=[CH:22][C:21]=3[C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][C:31]=3[O:36][CH3:37])[C@H:14]2[CH3:38])[CH:6]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:8]=1.[N+:41]([O-])([OH:43])=[O:42]>CC(O)=O>[F:40][C:2]([F:1])([F:39])[C:3]1[CH:4]=[C:5]([C@H:13]2[O:17][C:16](=[O:18])[N:15]([CH2:19][C:20]3[CH:25]=[C:24]([C:26]([F:28])([F:29])[F:27])[CH:23]=[CH:22][C:21]=3[C:30]3[CH:35]=[C:34]([N+:41]([O-:43])=[O:42])[CH:33]=[CH:32][C:31]=3[O:36][CH3:37])[C@H:14]2[CH3:38])[CH:6]=[C:7]([C:9]([F:11])([F:10])[F:12])[CH:8]=1

Participants

4

Reactant 2

HCID 944Nitric Acid2×HCID 11699822HCID 11699822, compound

Product 1

HCID 11614252HCID 11614252, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution of (4S,5R)-5-[3,5-bis(trifluoromethyl)phenyl]-3-{[2′-methoxy-4-(trifluoromethyl)biphenyl-2-yl]methyl}-4-methyl-1,3-oxazolidin-2-one (example 143) (159.4 mg, 0.276 mmol) in HOAc (5 mL) was added HNO3 (1.5 mL). After 45 minutes, additional HNO3 (1.5 mL) was added. 45 minutes later, the reaction was quenched by pouring into ice water (30 mL). The mixture was extracted with EtOAc (75 mL), and the organic layer was washed with 1 N NaOH, saturated NaHCO3, and brine (25 mL each). The organic layer was dried over Na2SO4, filtered, and concentrated. Purification of the residue by flash chromatography on silica gel (8 to 40% EtOAc/hexanes) afforded (4S,5R)-5-[3,5-bis(trifluoromethyl)phenyl]-3-{[2′-methoxy-5′-nitro-4-(trifluoromethyl)biphenyl-2-yl]methyl}-4-methyl-1,3-oxazolidin-2-one. Rf=0.11 (25% EtOAc/hexanes). LCMS=623.1 (M+1)+. 1H NMR (CDCl3, 500 MHz, rotamers present) δ 8.34 (m, 1H), 8.10 (m, 1H), 7.85 (d, J=6.9 Hz, 1H), 7.61-7.71 (m, 4H), 7.40 (m, 1H), 7.11 (m, 1H), 5.66 (d, J=8.0 Hz), 5.28 (d, J=8.2 Hz), 4.89-4.94 (m, 1H), 3.74-4.09 (m, 5H), 0.61 (d, J=6.6 Hz), 0.47 (d, J=6.5 Hz).

Workup

  1. custom45 minutes later, the reaction was quenched
  2. additionby pouring into ice water (30 mL)
  3. extractionThe mixture was extracted with EtOAc (75 mL)
  4. washthe organic layer was washed with 1 N NaOH, saturated NaHCO3, and brine (25 mL each)
  5. dry with materialThe organic layer was dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification of the residue by flash chromatography on silica gel (8 to 40% EtOAc/hexanes)

Sources & evidence

ORD record
ord-6a16eb38ef81428d8be7b34f60f15c80
Source dataset
uspto-grants-2014_05
Patent number
US08735435B2

Reaction notes

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